Supramolecular Liquid Crystalline Polymers

在过去的150年里，有机化学家一直致力于对共价键的理解。近年来，分子识别（由弱的非共价相互作用产生）的研究已被公认为是世界范围内重要的知识和技术前沿。Endo-（由会聚空腔产生）和exo（由类似大小和形状或表面的较大物体产生）分子识别、预组织和自组织为通过其组件的自组装自发产生功能超分子结构提供了基础。现在人们普遍认为，分子识别指导合成和自组装是生物系统产生和特性的关键。本研究旨在利用分子识别技术自组装合成超分子液晶聚合物并指导其相行为。将研究两类新型聚合物：利用类似烟草花叶病毒的原理自组装的功能超分子聚合物，以及环状主链聚合物，以及含有液晶环烷（即主链液晶低聚物的环状衍生物）受体作为结构单元的聚合物。第二类液晶聚合物将显示分子识别定向相变。预计本研究将产生自组装超分子合成离子通道等分子器件等各种系统，类似于自然生物系统，将选择性识别与外部调控相结合。最重要的是，这项研究将使我们在理解自然界使用的一些我们知之甚少的过程方面向前迈进一步，并将它们移植到合成超分子聚合物领域。

For the past 150 years, organic chemists were concerned with the understanding of the covalent bond. Recently, research on molecular recognition (generated by weak, non-covalent interactions) has been recognized worldwide as an important intellectual and technological frontier. Endo- (generated by convergent cavities) and exo (generated by larger bodies of similar size and shapes, or surfaces) molecular recognition, preorganization and self-organization provide the basis of spontaneous generation of functional supramolecular architectures via self-assembly from their components. It is now accepted that molecular recognition directed synthesis and self-assembly are responsible for the generation and properties of biological systems. This research aims to use molecular recognition both to self-assemble synthetic supramolecular liquid crystalline polymers and to direct their phase behavior. Two novel classes of polymers will be investigated: functional supramolecular polymers which self-assemble by using principles that resemble those of tobacco mosaic virus, and both cyclic main-chain polymers, as well as polymers containing liquid crystalline cyclophane (i.e., cyclic derivatives of main-chain liquid-crystalline oligomers) receptors as structural units. The second class of liquid-crystalline polymers will display molecular recognition directed phase transitions. It is expected that this research will produce molecular devices such as self-assembled supramolecular synthetic ion channels and various other systems which, by analogy with natural biological systems, will combine selective recognition with external regulation. Most important, this research will enable a step ahead in understanding some of the processes that nature uses and about which we know so little, and transplant them to the field of synthetic su pramolecular polymers.